Shot shell closure



O h 1942 J. HARMON SHOT SHELL CLOSURE INVETOR ATTORNEY Patented Oct. 27, 1 942 SHOT snau. oLosUaE Jesse Harmon, Wilmington, Del., assignor to Remington Arms Company Jnc a corporation of Delaware Application August 16, 1941, Serial No. 407,133

7 Claims. (oi. 102-42) This invention relates to shot shells, especially the closing thereof. More particularly, it appertains to the control of firing and ballistics by means of body closure seals which are easily applied and which do not cause objectionable barrelfouling.

The shot shell, as generally produced, comprises a fairly rigid paper cylinder (called the body) having over one end a metal cap (called the 'head). Ordinarily the head contains the propellent powder and means for igniting it. The body contains the shot charge and a partition (filler wad) separating it from the powder. It is universal commercial sealing practice to place a card (top wad) over the shot charge and fold the open edge of the body stock inwardly on top of the wad. It is self-evident that such a closure has substantially fixed resistance to opening. No part of it can be varied to control pressure or ballistics. This will be even more obvious when it.is appreciated that the properties of the body paper are fully determined by other considerations. This disadvantage cannot be overcome by changing the character of the top wad. A heavy, hard, unbreakable top wad interferes-with the movement of the shot, produces poor patterns, etc. Fragmentation of a frangible top wad results in a cloud of confetti-like" beads. These tend to obscure the target from the shooter and are blown into his face when the wind is 'from the general direction of the target. Such arrangements or features are obviously undesirable.

Shot shell bodies are made by rolling a specially prepared porous paper into tube form, the successive layers or convolutions of the paper being secured together by a starch adhesive. For protection against moisture and other purposes, the rolled tubes are heavily impregnated with a wax, usually paraffin wax, the wax content of the finished tube constituting not less than 20% of the weight of the tube. Since shot shells must fit rather closely in a gun chamber, the finished bodies must be brought to a given outside diameter with very low tolerances. For this pur- (2) the ballistic properties of the shell are improved; (3) the confinement and burning rate of the propellent powder are accurately controlled; (4) uniformity and improvement are obtained; and (5) loading economies are effected.

Another and more specific object was to provide a body seal which could be varied, coordinated and adapted to the burning characteristics of difierent propellent powders to more accurately control their confinement and burning rate, and to secure the benefit of the maximum energy available in the combustion thereof without the development of excessive pressures. Still other .objects were to seal a shot shell body with material which would not require special preparation of the body surface to receive the same, which would not cause fouling or clogging of the gun barrel even during rapid firing, and which would remain effective during long periods of storage even at temperatures somewhat above those normally encountered in the Temperate Zones. Yet further objects were to close the end of a shot shell with the body material in such a way that "blown patterns" are avoided and patterns better than those resulting from conventional shell closing, are obtained; to coordinate the strength of the body seal with the propellent powder utilized to provide a closure which would improve the ballistic properties of powders heretofore regarded as inferior or unsuitable; to secure standard velocities with reduced charges of powder and without the production of excessive pressures; and to provide an adhesive for bonding body seal discs to the waxed and ironed body papers which would enable the sealed shell ends to control both pressure and ballistics. A general advance in the art, and other objects which will appear hereinafter, are also contemplated.

The development of an adhesive suitable for use upon shot shell bodies is greatly complicated by the character of the material of these bodies pose the wax impregnated tubes are passed through a sizing die, which somewhat reduces their outside diameter, and in so doing irons the closure in such a way that (l) the necessity for a separate end closure (top wad) is eliminated;

for, as indicated above, in addition to the difflculties of eifecting adhesion to a waxed surface (a problem encountered in various arts) the method of manufacture results in a shot shell surface which is not only heavily waxed but, due

to the action of the sizing die, is smooth, hard,

" rigid, non-porous, etc.

unsealed aperture which remains when the end of the shot shell is closed by folding a considerable partof the end portion of the body inwardly, and to influence or govern the opening of the said folded end.

The aforementioned "phenol rubber product," generally known as "Phenol Rubber Product 2,158,530, is obtained when rubber isworked on a rubber mill (or related apparatus such as a Banbury mixer) with about 5% to 55% of its weight of beta-naphthol (or similar monohvdric phenol) in they presence of a small amount of a special catalyst, for example, dihydroxy-fluoroboric acid or sulfuric acid,'for about minutes at 100 C. This material is quite unlike rubber and the heretofore known rubber derivatives (including the products known as rubber isomers) The new material, being denser, sinks when placed in water, will not adhere to rubber, is more soluble in hydrocarbon solvents than cyclized rubber (J. I. E. C. XIQCUI 389), and when mixed with rubber on a mill and the mixture made into a thin cement, layers off. It seems to be an alkylated phenol (rubber being the alkylating agent) since the phenol molecule seems to have chemically combined with the rubber molecule (probably at what was an unsaturated carbon atom in ordinary rubber).

How the foregoing objects and related ends are accomplished will be apparent from the following exposition in vwhich are disclosed the principle and divers embodiments of the invention, including the best mode contemplated for carrying out the same.. Parts are given by weight shell is closed by folding in the end portion of the body. This is carried out by first forming in that press the segments I3 (between the creases 12) into aplane. This brings about a. substantially complete closing of the body:

Exhaustive tests have shown that it is definitely detrimental to indent the end closure very much, so it is preferred that the flat closure: portion bein the plane of the end of the side wall,

as illustrated in Figure 4, or only very slightly inset, as shown at 53 in Figure 5." In these figures, in the interest of clarity, the shot charge has not been shown. The creased end portion of the body is shown as extending downwardly within the shell at 45.

When the shell is closed in the manner just described, there remains at the center. (or cylindrical axis) an unsealed juncture 5! for which a seal is desirable. To provide such a seal, a disc 5|, of paper or similar material as illustrated in Figures 4, 5 and 6, is employed. The principal novelty of this invention is in the composition of the adhesve layer ll, used to secure the sealing throughout the application unless otherwise been subjected to the final closing operation and is fully closed; 7

Figures 4 and 5 are sectional elevation views taken along the diameter of the closed and sealed end portions of shot shell bodies, showing the v sealing means applied in accordance with this invention; I

Figure 6 is a perspective view of that portion of the closed and sealed (finished) shot shell.

body illustrated in Figure. 5 and Figure '7 is a fragmentary perspective view of the open end of a fired shell having segmentlike pieces still adhering thereto.

' Similar characters refer to similar parts throughout the drawing.

In Figure lthere is illustrated a conventional shot shell comprising a body -H and a head 2i.

The body is a waxed cardboard tube and the head a brass thimble-like structure. Within the headis a base wad 22, a battery cup 23, a primer cup 24, an anvil 25 and a; charge of priming composition 26.

When in shells of this type the priming composition is ignited, as by striking the primer cup with a firing pin, thefiame thereof ignites the charge of propellent powder 39. Before firing, an over powder wad 32 and one or more "filler" wads 33 separate the powder 3i from the shot constituting the charge 35.

In the present invention the end of the shot disc to the body closure.

It will be obvious that by proper selection (of paper 6!) and regulation of adhesive strength of the layer 4|, there can be secured any degree of "confinement" of the shell contents (includ-' ing the propellent powder) up to the limit of the tensile strength of the body material (paper, etc.) An accurate control of ballistics thus becomes possible. Unfortunately the strength of suitable adhesives decreases with time, so that the aforementioned control of ballistics is dependent upon adhesive which does not begin" to weaken for'long periods of time. An advantage of this invention is'illustrated in Figure 6 by the indicia 62. This may indicate the size and character of the shot contained n the shell. Conventional shot shell closures provide no means for accomplishing this purpose.

When the shot shell of this invention is fired. both the adhesive and paper layers (4| and GI) are ruptured as the body straightens to substan-' tially its original cylindrical form. Segment-like portions 6, H2 and GI} of. the disc 6| remain securely affixed ure 7. I

Specific examples of the new adhesive compositions, and shot shells embodying the same, follow. i

Example I A shot shell having a body surface of heavily waxed, very smooth, non-porous paper, was loaded. The open end was then partially closed by to the body, as shown in Fig- K of U. S. A. Patent No. 2,158,530, and 6.2, parts of phenol formaldehyde methylamine resin prepared according to Example I of U. S. nsPatent 2,098,869, were-dissolved in 81.2 parts of toluene. Paper (35 pound sulfite type) slightly heavier than ordinary typewriter paper stock, was coated on one side with the resulting composition, and the solvent removed. The adhesive layer obtained was 0.002 to 0.903 of an inch thick. A disc of suitable size was stamped from the coated paper and secured to the folded end of the shot shell by means of heat and pressure.

Example II Carry out the sealing of shot shells in the man-' ner described in Example I, with an adhesive prepared from beta-naphthol rubber product 25 parts, poly-beta-dimethyl-amino-ethyl methacrylate 6.2 parts, and toluene 81.2 parts.

Example III ner described in Example I, with an adhesive prepared by mixing until homogeneous a solution of 50 parts of beta-naphthol rubber product in 150' parts of toluene anda solution of 2.6 parts of amine dimethylol urea-dimethyl ether resin (preparation described under Group K) dissolved in parts of dioxan to 8 parts of beta-naphthol rubber product dissolved in 24 parts of toluene.

Example IX sealing paper by conventional means, such as Carry out the sealing of shot shells in the manbrushes, rollers. doctor knives, etc., after which the solvent is allowed to evaporate. The films thus deposited are non-tacky, waterproof and flexible. They are not adhesive in the dry condition at ordinary temperatures, but when'moistened with hydrocarbonsolvents such as toluene. or when subjected to heat and pressure. as used in conventional sealing procedures, they have ex.- cellent adhesion to materials like the smooth. waxedand ironed cardboard commonly employed for shot shellbodies.

The ratio of phenol-rubber product to amino polymer may be varied over a wide range. depending upon the specific adhesive requirements. in general the more amino polymer is used the greater will be the storage life of .the adhesive composition, that is to say. the stabilizing efi'ect' is roughly proportional to the amount used with the phenol-rubber product. Compositions conthe resinous reaction. product of phenol, formaldehyde and methyl amine (see Example lID' dissolved in 5 parts of toluene.

Example V carry out the sealing of shot shells in theman- Example VI Carry out the sealing of shot .shells in the' taining as low as 25% of phenol rubber product gradients of the stabilized composition are permissible.

The phenol rubber products are resinous, transparent, thermoplastic, benzene-soluble derivatives of rubber which are resistant to acids and alkalies, which do not adhere to rubber,

manner described in Example I, with an adhesive prepared by mixing until homogeneous a solution of 40 parts of beta-naphthol rubber product in 120 parts of toluene and a solution of 10 which have an impact strength similar to phenol aldehyde resins; which impart a hardness to rubber (when compounded therewith) like glue parts of triethanol amine phthalate product' (preparation described under Group G) in 90 parts of dioxan.

Example VII Example VIII Carry out thesealing of shot shells in the manner described in Example I. with an adhesive and rnontan'wax, and which are obtained by reacting rubber with a monohydric phenol which contains no substituents other than halogen and hydrocarbon radicals. The phenol rubber products can be hydrogenated at temperatures in the range 80-200 C. in the presence of an acidic catalyst.

The preparation of the phenol rubber product is described in U. S. A. Patent No. 2,158,580 (Williams), and in the interest of brevity, reference is made thereto for details. For convenience it may be pointed out that the amount prepared by adding 2 parts at n-butyl-diethanolplayed in compounding shot shell adhesives. 'Almany of the specific examples, it is to be understood that any one or a plurality of the products disclosed in said patent may be employed, when desired.

The crude product (containing excess phenolic material) is preferred for use'in shot shell adhesive compositions, but good results have been obtained when the excess of the phenol was removed. Ordinary extraction procedures utilizing such materials as alcohol solvents, such as ethanol and butanol, are suitable for removing the unreacted phenolic material. The reaction product may also be purified by dissolving in toluene and precipitating the phenol rubber product with ethyl alcohol (which retains the phenolic body insolution). Treatment of the crude reaction product with formaldehyde renders the excess phenolic material innocuous by causing it to form. a phenol formaldehyde resin, whose'p'resence in the composition is not ordinarily objectionable (because it does not exude or blush out as the free phenolic compound would).

Various phenols in addition to the hydroxybenzene and beta naphthol of the examples, for

instance chloro-phenol, c'resol and dihydroxy diphenyl, may be employed in the manufacture of the phenol rubber product, as indicated in the patent just discussed. One or more phenolic materials may be used in the reaction with the rubber. Catalysts other than the sulfuric acid and dihydroxy-fluor-boric acid, for example, or-

ganic sulfonic acids, hydroxy-fluorboric acid and boron trifiuoride, maybe employed.

The phenol rubber products of this invention may be designated by a, variety of names other than those already mentioned, for example, rubber alkylated phenol, phenol modified rubber, rubber substituted phenol" and .phenol rubber condensation product, The terminology employed is intended to apply only to thetype of material obtained according to the aforementioned U. S. A. Patent No. 2,158,530. These names are not to be construed broadly enough to cover isomers or like derivatives of rubber which might-be obtained by using phenol or phenol sulfonic acid in a simple catalytic capacity.

The amino-nitrogen-containing polymers ca pable of being formed into coherent films, soluble in organic solvents and in.2% aqueous acetic acid and insoluble in water can, for convenience,

be divided into sub-groups,'as followsz.

- (A) Resinous polymeric 'coherent-fllm-forming reaction products of phenols, aldehydes and man terial from the group consisting of ammonia,

primary-amines and secondary amines;

2,800,367 'though' this type of material wasemployed in reaction products of diaryl (especially diphenyl) guanidine with aldehydes (especially formaldehyde) and amines (primary orsecondary);

(B) Resinous polymeric coherentrfllm-forming T *aminoalcohol estersof material from .the group consisting of acrylic acid and acrylic acid substituted in the alpha position by a hydrocarbon radical;

(C) Resinous polymeric coherent-film-forming reaction products of amino phenols with aldehydes;

(D) Resinous polymeric coherent-fllm-forming reaction products of alphybketonesf'(aliphatic and alicyclic) with formaldehyde and material from the group consisting of ammonia, primary.

amines, secondary amines and tertiary, amines; (E) Resinous polymeric coherent-film-forming reaction products of diaryl (especially diphenyl) guanidine with aldehydes, (especially formaldehyde); v (F) Resinous polymeric-coherent-flim-forminz (G) Resinous polymeric coherent-film-forming amino alcohol esters of polycarboxylic acids;

(H) Resinous coherent-film-forming aromatic amine aldehyde resins;

formaldehyde, and lower aliphatic (in which the substituent radicals have less than 5 carbon atoms) primary or secondary amines,-especially methyl, dimethyl, butyl and dibutyl amines;

(N) 'Resinous polymeric coherent-film-forming products obtained by polymerizing, in the presence of catalytic proportions of stannic chloride, the reaction product of .epichlorohydrin, with material from the group consisting of ammonia and primary aliphatic amines;

(O) Resinous polymeric coherenteiilm-forming reaction products of phenol-lignin with dimethyl amine and formaldehyde;

(P) Resinous polymeric coherent-film-form- 'ing products obtained by the catalytic hydrogenation of resins having ketone groups at superatmospheric temperature and pressure in the presence of material from the group consisting of ammonia, primary amines and secondary amines; and 1 (Q) Resinous polymeric eoherent-film-form- "ing reaction products of protein 'material from the group consisting of lower aliphatic aldehydes and'lower aliphatic ketones and amines having less than 9 carbon atoms, in which the amino nitrogen is joined to the aliphatic carbon.

These related highly polymeric amino nitro-' gen-containing substances, which are prepared synthetically, form a distinctive group.. Since the corresponding monomers do not accomplish the end desired, it is clear that their efiectlveness is dependent upon polymeric form.'

Details of the preparation of these basic amino nitrogen-containing polymers are summarized below.

In, general, the products of group A are prepared by reacting an aldehyde v(preferably'formaldehyde) with the appropriate nitrogen compound (ammonia or amine) in aqueoussolution to givea methylolderivative (of the ammonia or amine), which is' then reacted with the'phenol in question. The resin separates from the solution' as it is formed, and is usually washed with water before drying. The detailed preparation of these'resinsis disclosed inlthe patent litera-' time, see for example, U. S. A. Patent No. 2,098,869

(Harmon & Meigs) particularly Examples A-l, A- -T-and A 8, U. S. A. PatentNo. 2,168,335 (Heckert), particularly Example A6, U... S.. A.

. Patent No. 2,168,336 '(Heckert), particularly Example, 4-2, U. s. .A. Patent No. 23031.55! (Bruson) ,and U. S. A. Patent No. 2,053,092

(Bruson). The preferred combinations are the reaction products of:

(1) Phenol 1 Formaldehyde 2 v Methylamine 1 (2) Phenol 0.5 Formaldehyde. 1.4 Dimethylamine 0.4 Ammonia 0.5

(3) Phenol 1. 1

Formaldehyde--. 2

Piperazine 1 (4) Beta-naphthol 1 Formaldehyde 2 V Methylamine 1 (5) Phenol 1 Formaldehyde 2 N-aminoethyl morpholine 1 (s) Phenol 1 Formaldehyde 2 Ammonia 1 (7) Phenol 1 Formaldehyde 2 Ethylene-diamine 1 (8) Resorcinol 1 Formaldehyde 1 Methylamine 0.5

(9) Diphenylolpropane 1 Formaldehyde 4 Dimethylamine 2 (10) Xylenol 1 Formaldehyde 1.8 Diethanolamine 0.6

In general the polymeric amino nitrogen -containing bodies of group B are prepared by reacting the appropriate amino alcohol with the methyl ester of the acrylic (or alpha-substituted homolog, preferably methacrylic) acid, distilling off the methanol (thereby forming the monomeric amino alcohol acrylate or homolog), and

polymerizing (by any suitable means, such as amino-phenol with formaldehyde.

The resinous products of group D are, in general, prepared in the same manner as the preferred materialwvhich is the reaction product of acetone, formaldehyde and methylamine. To prepare this material, a solution of 5 parts of trisodium phosphate (NasPOrlZHzO) in 50 parts of water was'mixed with 50 parts paraformaldehyde. The mixture was cooled in ice, and a solution containing'19 parts (0.61 mol) of methylamine dissolved in 50 parts of acetone, added. A vigorous reaction set in, and cooling was neces+ sary. After the initial reaction was over, the

mixture was heated on a steam bath over a reflux condenser for 1% hours. It was then allowed to stand overnight. A soft brown, resinous mass resulted. This was well mixed with water The resinous products of group E are in general prepared in the same manner as the preferred material which is the reaction product of diphenyl guanidine with formaldehyde. To prepare this material, 43 parts (0.2 mol) of diphenyl guanidine was mixed with 48.6 parts (0.6 mol) of 37% formaldehyde solution, and the mixture allowed to stand with occasional stirring for 18 hours at a temperature of 50 C. The mixture set to a;

sticky, taffy-like mass which became progressively harder and more brittle. After '18 hours, the resinous mass was ground under cold water, filtered, washed with water and air dried. The final product was a white, amorphous powde'r soluble in dilute (2%) acetic acid and toluene.

The polymeric basic amino nitrogen-containing bodies of group F are in general prepared in the same manner as the preferred material which is the reaction product of diphenyl guanidine, formaldehyde and methylamine. To prepare this material, a solution of dimethylol methylamine (1 mol) in water was made by passing 31 parts (1 mol) of methylamine into 160 parts (2 mols) 'of 37% formaldehyde solution cooled with ice. The

' solution was added to 215 parts (1 mol) of diphenyl guanidine, and the mixture stirred for 15 minutes. This gave a dough-like product which was allowed to stand for 22 hours to complete the reaction. At the end of this time the mixture became a hard, resinous mass. It was ground under cold water, filtered, washed with water, and dried over calcium chloride in a vacuum desiccator. The reaction product was a white powder soluble in acetone, ethyl acetate, chloroform, dioxan and toluene.

The resinous products of group G are, in general, prepared in the same manner as the preferred material which is the reaction product of triethanol amine and dimethyl phthalate. To prepare this material, a mixture of 149 parts (1 mol) of triethanol amine, 194 parts (1 mol) of dirnethyl phthalate and 800 parts of benzene was charged into a reaction flask, and a solution of 2 parts of sodium in 16 parts of methanol was added in small proportions during the course of the reaction as a catalyst. The mixture was heated at a temperature of 130155 C. for 9 hours. During this time a binary of methanol and benzene distilled off. When the theoretical amount of binary had been collected in the receiver, the reaction was stopped and the benzene distilled off on a steam bath under reduced pressure. The residue was a viscous oil which, upon cooling, became a soft, resinous mass. The resinous product was soluble in 20% acetic acid, and films fiowed from this solution became hard and brittle .on baking at 110 C. for 10 hours. The'resinous reaction product was soluble in dioxan, 90% ethyl alcohol, acetone and'chloroform, and was partly soluble in toluene.

Preparation of the resins falling in category H is described in detail in British Patent 342,325.

The preferred reaction product in this group is 1 the reaction and the products are described in detail in U. S. A. Patent No. 2,122,707 (Balthis) The resinous products of group J are in general prepared in the same manner as the preferred material which is the reaction product of formaldehyde, piperazine and phenol. To prepare this material, 162 parts (2 mols) of aqueous -37% formaldehyde was cooled to C., and 190 parts (1 mol) of'piperazine hexahydrate in 200 parts of.

water added drop-wise at such a rate that the temperature did not rise above 23 C. The reaotion vessel was cooledin ice, then 94 parts (1 mol) of phenol in parts of water was added all at once and the ice bath removed. The reaction vessel was then raised to a. temperature of C. and allowed to stand over night. A light pink, sticky resin,- which was washedwith water, was obtained.

The polymeric substances of group X are, in

. general, prepared in the same manner as the preferred materials which are the reaction products of dimethylol urea dimethyl ether with n-butyl-diethanol amine and with hexamethylenediamine.

To prepare the first of these materials, 80.5 parts ofn-butyl-diethanol amine and 74 parts of dimethylol urea dimethyl ether were mixed and heated in an atmosphere of nitrogen in a bath maintained at 150-160 C. for 1.5 hours. Methanol (28 parts) was evolved during this time, and a clear, light-yellow resin, soluble in dioxan, triscribed 'in U. S. A. Patent NO.

(Greenewalt). V

The amine polymers of group Q are, in general, prepared in the same manner as the preferred species whose properties and mode of preparation are disclosed inU. S. A. Patent No. 2,143,023 (Meigsln Instead of simple polymers, interpolymers may be prepared, for instance, by reacting methyl methacrylate and methyl vinyl ketone in the presence of ammonium hydroxide or reacting beta-dicyclohexyl-aminoethyl methacrylate monomer and beta-dimethylaminoethyl methacrylate monomer together under suitable conditions, or reacting dicyclohexylaminoethyl methacrylate with Meigs) chlorethylene, dilute aqueous acetic acid and hydrochloric acid, was formed.

To prepare the second of these products, 29

parts of hexamethylene diamine and 37 parts of dimethylol urea dimethyl ether were mixed and gently heated in a distilling vessel in an oil bath until 7 parts of methanol had distilled. The

resinous residue in the distilling vessel was washed with water, dissolved in concentrated hydrochloric acid, and precipitated with aqueous sodium hydroxide. The precipitate was filtered, washed with water and dried. A white, amorphous powder, which was soluble in butanol and dilute aqueous acetic acid, was obtained.

The resinous products of group L are prepared, for example, by dissolving 15 parts of di-n-butylamine and 10 parts of polymeric vinyl-alphachloroacetate in 80 parts of ethylene glycol-monomethyl ether, allowing the solution to stand in a closed vessel for 2 weeks, pouring into 350 parts of water, filtering ofi the resin which separates, and drying it. The product prepared in the manper just described is an orange-colored rubbery v mass soluble in acetone, ethanol and toluene and in 2% aqueous acetic acid. About. 13 parts are by the process of Example B of .U. S. A. Patent No. 2,122,433.

The coherent-film-forming resinous products of The latter products, which are dilute acetic acid soluble resins, and with which may be classed the very satisfactory phenol formaldehyde piperazine resins-are obtained by reacting a phenol .c'ontainingcarbon, hydrogen and oxygen only,

' and having at least 2' unsubstituted nuclear positions ortho or para to the phenolic hydroxyl with formaldehyde and a non-aromatic primary amine containing less than 7 carbon atoms. A molecular ratio of amine t'o phenol of not less than 0.5: 1 and not greater than 1:1,- and a molecular ratio of aldehyde to amine not greater than 1:1 in this reaction, give especially desirable results.

The specific compounds which are preferred for the purposes ofthis invention, are beta-dl-nbutylaminoethyl methacrylate polymer; 2-aminocyclohexyl. methacrylate polymer; triethanolamine mono-methacrylate polymer; 2-(diethylamino) -cy'clohexyl methacrylate polymer; 4- (beta-methacrylyloxyethyl) morpholine polymer; beta-dimethylaminoethyl methacrylate polymer; beta-diethylaminoethyl acrylate polymer; betadlcyclohexylaminoethyl acrylate polymer; 1- (beta-methacrylyloxyethyl) piperidine polymer; the resin obtained by the hydrogenation, in the presence of ammonia, of polymerized bis-(4- ketocyclohexyl) dimethylmethane; the resin obtained from the hydrogenation, in the presence of ammonia, of polymerized methylvinyl ketone; the reaction product of polymeric methyl alphamethylvinyl ketone and cyclohexylamine; the reaction products of polymeric methylvinyl ketone and aqueous ammonia (or cyclohexylamine, ethylenediamine, hexamethylenediamine, and the like); the resin obtained by reacting cyclohexanone with formaldehyde and methylamine; the resinous reaction product of acetone with formaldehyde and butylamine, and phenol-formaldehyde-hydrazine resin, cresol-formaldehyde-tetragroup P are, in general, prepared in the same ethylenepentamine resin, phenol-formaldehydeethylenediamine 'resin, phenol-formaldehydedodecylamlne resin, phenol-formaldehyde-thiourea resin and cresol-formaldehyde-melamine resin. i

The polymeric basicv amino nitrogen-containing substance may be introduced into the phenol L rubber product and compositions containing the same, in any desired manner. Ordinarily the incorporation is made by the use of a mutual solvent or by milling, but grinding, kneading, and other conventional mixing procedures are satisfactory.

The adhesive compositions may be applied to the ammunition parts (paper or other medium) as solutions (used in 'a broad sense to include both true solutions and pseudo-solutions, which latter are in reality colloidal suspensions), emulsions, melts without any solvent, and melts with;

reduced amounts of solvent.

In forming solutions and melts containing small amounts oforganic liquids of the phenol rubber product-amino polymer compositions, aliphatic, aromatic and chlorinated hydrocarbonsare suitable. The preferred substances 'are benzene, toluene, xylene, tetrachlorethane, kerosene and related products.

In preparing the adhesive compositions, various adjuvants or augmenting agents, such as resins, plasticizers, waxes, colors, etc., may be incorporated when desired.

The preferred resins (natural, synthetic and semi-synthetic) include rosin, hydrogenated 'rosin, hydrogenated rosin derivatives, ester gum,

pitches, cumarone indene resins, alkyd (polyhydric alcoliol-polycarboxylic acid reaction product) resins, damar, and the like. Such materials, individually and in combination, compound readily with the phenol rubber product. Although resins generally improve homogeneity and thermoplasticity, it is not always desirable to have a resin present. When the presence of resins is desirable, one or more may be used.

The preferred plasticizers (sometimes improperly referred to as softeners) are dibutyl phthalate, tricresyl phosphate, chlorinated paramn, dixylyl ethane, chlorinated diphenyls, hydrogenated methyl abietate, diethyl-toluene sulfon-.

the shell body and dried before sealing instead of to the sealing disc, or may be applied to both, as convenience may dictate.

The shell bodies and sealing discs may be made of materials other than paper, for example, re-

generated cellulose, if desired.

The molecular weight of the amino'polymer (basic resin) has some eifect on its power to stabilize the phenol rubber product. Resins giving low viscosity solutions at high (50%) solids contents, are preferred. These factors should be taken into consideration in compounding the adhesive, it being desirable, for example, to utilize resinous materials of high softening point to aid in producing adhesive compositions of high softening points, and vice versa.

Many of the advantages of the present invention are apparent from the foregoing part of the specification. The bond between the shell body surface (waxed cardboard) and the sealing disc (paper) remains flrm at temperatures which are reached at rapid firing (up to 120 F.49 0.).

- The adhesive and sealing disc remain firmly secured to the shot shell body after firing, so that no deposit or residue accumulates .in the gun barrel, The adhesive composition'seals the Juneture of the folded closure against the entrance of and loaded material to effect loading economies and improved ballistics.

The sealing means has thermoplasticcharacteristics and adheres to the shell material with adequate and controllable tenacity. The adhesive of this invention elimihates the necessity for special treatments of the shot shell body such as abrasion, roughening of the surface, removal of a substantial portion of the waterproofing oil contained in the surface, etc., to facilitate penetration by theadhesive. The adhesives of the present invention do not have objectionably low softening points, and are able to withstand shock. Approximately a 25- fold improvement in adhesive ageing life (at C.) is hereby obtained. The adhesives do not have to be used when freshly prepared.

As many apparently widely diflerent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A shot shell comprising a. body, an end closure integral with said body, and a moistureproofing and ballistic controlling member seal secured to said end closure, said seal comprising essentially a thin disc adhesively secured to said end closure by means of phenol rubber product diluted with a small amount of basic amino polymer capable of being forced into coherent solid films which are substantially insoluble in water and 5% aqueous ammonia and soluble in 2% aqueous acetic ,acid and organic solvents, said phenol rubber product being a reaction product of rubber and one or more phenols, contain- .ing 1% to 5% of the phenol material chemically combined with the rubber which is resinous,

thermoplastic, benzene soluble, acid resistant,

end closure by means of beta-naphthol rubber product containing 2%-75%.of basic amino polymer capable of being formed into coherent solid films which are substantially insoluble in water and 5% aqueous ammonia and soluble in 2% aqueous acetic acid and organic solvents, said naphthol rubber product being a reaction product of rubber and one or more phenols, containing 1% to 5% of the phenol material chemically combined with the rubber which is resinous, thermoplastic, benzene soluble, acid resistant, alkali resistant, which does not adhere to rubber, which has an impact strength similar to phenol aldehyde resins and which imparts a hardness to rubber like glue.

3. A shot shell body comprising, an end closure integral with the side wall thereof, said end being sealed with beta-naphthol rubber product containing 25% resinous. reaction prodnot of phenol, formaldehyde and methylamine,

chemically combined with the rubber which isresinous, thermoplastic, benzene soluble, acid resistant, alkali resistant, which does not adhere to rubber, which has an impact strength similar to phenol aldehyde resins and which imparts a hardness to rubber like glue.

4; In a shot shell, the combination comprising a substantially cylindrical body of wax impregnated deformable. material and an exteriorly planar end closure integral with said body and flush with the end thereof. and comprising a plurality of abutting segments and folds joining said segments, said closure including the segments and folds being integral with said body, and aseal for said end closure comprising essentially a thin disc adhesively secured to said end closure by means of phenol rubber product diluted with a a small amount of basic amino polymer capable of being. formed into coherent solid films which are substantially insoluble in water and 5% aqueous ammonia and soluble in 2% aqueous acetic acid and organic solvents, said phenol rubber product being a reaction product of rubber and one or more phenols, containing 1% to 5% of the 'phenol material chemically combined with the rubber which is resinous, thermoplastic, benzene soluble, acid resistant, alkali resistant, which does not adhere to rubber, which 'hasan impact strength similar tophenol aldehyde resins and which imparts a hardness to rubber like glue.

5. In a shot shell, the combination comprising a substantially cylindrical body of wax impregnated deformable material and an exteriorly planar end closure integral with said body and flush with the end thereof, and comprising a pluwith the rubber which is ,resinous, thermoplastic, benzene soluble, acid resistant, alkali resistant, which does not adhere to rubber, which has an impact strength similar to phenol aldehyde resins and which imparts a hardness to rubber glue. Y

6. In a shot shell, the combination comprising a substantially cylindrical body of wax impregnated deformable material and an exteriorly planar end closure integral with said body and flush with the end thereof, and comprising a2 plurality of abutting segments and folds joining said segments, said closure including the seg-' ments and folds being integral with said body, and a seal for said end closure comprising essentially a thin disc adhesively secured to said end rality of abutting segments and folds joiningv said segments, said closure including the segments and folds being integral with said body, and a seal for said end closure comprising essentially a thin disc adhesively secured to said end closure by means of beta-naphthol rubber prodnot containing 2%-'l5% of basic amino polymer capable of being formed into coherent solid films which are substantially insolublein water and 5% aqueous ammonia and soluble in 2% aqueous acetic acid and organic solvents, said naphth'ol rubber product being a reaction product of rubbar and one or more phenols, containing 1% to 5% of the phenol material chemically combined closure by means of beta-naphthol rubber prodnot containing 25% resinous reaction product of phenol, formaldehyde and methylamine, said naphthol rubber product being a reaction product a I of rubber and one or more phenols, containing 1% to 5% of the phenol-- material chemically combined with the rubber which is resinous, thermoplastic, benzene'soluble, acid resistant, alkali resistant, which does not adhere to rubber, which has an impact strength similar to phenol aldehyde resins and which imparts a hardness to rubber like glue.

7. In a shot shell, the combination comprising formed into coherent solid films which are substantially insoluble in water and 5% aqueous ammonia and soluble in 2% aqueous acetic acid and organic solvents, said phenol rubber product being a reaction product of rubber and one or like v 

